Adhesive compositions containing epoxy resin, carboxyl containing copolymer and 2,2,-bis-(4-hydroxyphenyl) sulfone

ABSTRACT

The disclosure describes new adhesive compositions having improved toughness and excellent high temperature shear strength comprising the reaction product of a major amount of a polyepoxide with a minor amount of a reactive carboxyl group containing polymer and 2,2-bis(4-hydroxyphenyl)sulfone.

United States Patent Klapprott et al. [4 1 July 18,1972

1541 ADHESIVE COMPOSITIONS CONTAINING EPOXY RESIN, Refer nces CitedCARBOXYL CONTAINING UNITED STATES PATENTS COPOL R AND ZL'BIS'M. 2 94733s 8/1960 R d 260/836 e1 HYDROXYPHENYL) SULFONE 3,030,332 4/1962Lombardi ...260/836 [72] Inventors: David K. Klapprott; Daniel L.Paradis, 3,312,754 1967 M s ---2 0/83 both of Concord, Calif. 3,367,9902/1968 Bremmer ..260/831 [73] Assignee: The Dexter Corporation,Pittsburg, Calif. Pn-mary Examiner paul Lieberman [22] Filed: Sept. 10,1970 Attorney-Fulwider, Patton, Rieber, bee & Utecht [21] App]. No.:71,269 57 ABSTRACT The disclosure describes new adhesive compositionshaving [52] US. Cl ..260/837 R, 260/2815 AS, 260/285 B, improvedoughness and excellent high temperature Shear 260/285 D, 260/31.6,260/328 EP, 260/332 EP, strength comprising the reaction product of amajor amount of 260/33-4 260/336 EP, 260/33-8 260/47 a polyepoxide witha minor amount of a reactive carboxyl 260/47 EN, 260/830 Tw, 260/836-156/330, group containing polymer and 2,2-bis(4-hydroxyphenyl)sul-161/184, 161/185, 161/186 f [51] Int. ....C08g 45/04 [58] Field ofSearch ..260/836, 837 15 Claim, No Drawings ADHESIVE COMPOSITIONSCONTAINING EPOXY RESIN, CARBOXYL CONTAINING COPOLYNIER AND2,2,-BIS-(4-HYDROXYPHENYL) SULFONE BACKGROUND OF THE INVENTION Thepresent invention relates to novel polyepoxide compositions. Moreparticularly the present invention relates to a novel polyepoxidecompositions useful as adhesives.

Good adhesive and laminating properties can generally be obtained fromadhesives made with polyepoxide resins. While many of these adhesivesshow excellent textile shear strength at ambient temperatures, suchshear strengths rapidly decrease with increasing temperature. Theaircraft and aerospace industries have long sought an adhesivecomposition suitable for use where high temperature, i.e., 250F, shearstrength and toughness are necessary.

SUMMARY OF THE INVENTION The present invention relates to anepoxy-containing composition comprising the acetone soluble reactionproduct of a major amount of a polyepoxide and a minor amount of areactive carboxyl group containing polymer and 2,2-bis(4-hydroxyphenyl)sulfone.

The present invention also relates to a process for preparing an acetonesoluble epoxy-containing composition which comprises reacting a majoramount of a polyepoxide with a minor amount of a reactive carboxyl groupcontaining polymer in the presence of from 0.05 to 3 percent by weightof the reactants of a catalyst selected from the group consisting oftertiary amines, quaternary ammonium salts, organo-substitutedphosphines and phosphonium halides and a minor amount of 2,2- bis(4-hydroxyphenyl)sulfone.

DESCRIPTION OF THE INVENTION The polyepoxides to be used in preparingthe compositions of the present invention comprise those materialspossessing more than one vicinal epoxy group, i.e., more than one group.These compounds may be saturated or unsaturated, aliphatic,cycloaliphatic, aromatic or heterocyclic and may be substituted withsubstituents, such as chlorine, hydroxyl groups, ether radicals and thelike. They may be monomeric or polymeric.

For clarity, many of the polyepoxides and particularly those of thepolymeric type are described in terms of epoxy equivalent values. Themeaning of this expression is described in U.S. Pat. No. 2,633,458. Thepolyepoxides used in the present process are those having an epoxyequivalency greater than Various examples of polyepoxides that may beused in the process of the invention are given in US. Pat. No. 2,633,458and it is to be understood that so much of the disclosure of that patentrelative to examples of polyepoxides is incorporated by reference intothis specification.

Other examples include the epoxidized esters of polyethylenicallyunsaturated monocarboxylic acids, such as epoxidized linseed, soybean,perilla, oiticia, tung, walnut and dehydrated castor oil, methyllinoleate, butyl linoleate, ethyl l, l2-octadecadienoate, butyl9,l2,l5-octadecatriencate, butyl eleostearate, monoglycerides of tungoil fatty acids, monoglycerides of soybean oil, sunflower, rapeseed,hempseed, sardine, cottonseed oil, and the like.

Another group of epoxy-containing materials used in the process of theinvention include the epoxidized esters of unsaturated monohydricalcohols and polycarboxylic acids, such as, for example,di(2,3-epoxybutyl) adipate, di( 2,3-epoxybutyl)oxalat e,di(2,3-epoxy-hexyl)succinate, di(3,4-epoxybutyl)maleate,di(2,3-epoxyoctyl)pimelate, di(2,3-epoxybutyl)phthalate,di(2,3-epoxyoctyl)tetrahydrophthalate, di(4,5- epoxydodecyl)maleate,di(2,3-epoxybutyl)terephthalate,

di( 2,3-epoxypentyl)thiodipropionate, di( 5,6-epoxytetradecyl)diphenyldicarboxylate, di(3,4-epoxyheptyl)-sulfonyldibutyrate, tri(2,3-epoxybutyl l ,2,4-butanetricarboxylate,di(5,6-epoxypentadecyl)tartarate, di(4,5-epoxytetradecyl)maleate,di(2,3-epoxybutyl)azelate, di(3,4-epoxybutyl)citrate, di(5,6-epoxyoctyl)cyclohexane-l, 2dicarboxylate, di(4,5-epoxyoctadecyl)-Malonate.

Another group of the epoxy-containing materials includes thoseepoxidized esters of unsaturated alcohols and unsaturated carboxylicacids, such as 2,3-epoxybutyl-3,4 -epoxypentanoate, 3,4-epoxypentanoate,3,4-epoxycyclohexyl-3, 4- epoxycyclohexanoate,3,4-epoxycyclohexyl-4,5-epoxyoctanoate,2,3-epoxycyclohexylmethylepoxycyclohexane carboxylate.

Still another group of the epoxy-containing materials includesepoxidized derivatives of polyethylenically unsaturated polycarboxylicacids, such as, for example, dimethyl 8,9, l 2, l3-diepoxyeicosanedioate, dibutyl 7,8, l l, l 2-diepoxyoctadecanedioate,dioctyl I0, I ldiethyl-8,9, l 2, l 3-diepoxyeiconsanedioate, dihexyl6,7, l0,l l-diepoxyhexadecanedioate, didecyl 9-epoxyethyl- 10, ll-epoxyoctadecanedioate, dibutyl 3-butyl-3,4,5,6-diepoxycyclohexanel,2-dicarboxylate, dicylohexyl 3,4,5 ,6-diepoxycyclohexanel,2-dicarboxylate, dibenzyl l ,2,4,5-diepoxycyclohexanel ,Z-dicarboxylateand diethyl 5,6,10, 1 l-diepoxyoctadecyl succinate.

Still another group comprises the epoxidized polyesters obtained byreacting an unsaturated polyhydric alcohol and/or unsaturatedpolycarboxylic acid or anhydride groups, such as, for example, thepolyester obtained by reacting 8,9,12,13- eicosanedienedioic acid withethylene glycol, the polyester obtained by reacting diethylene glycolwith 2-cyclohexene- 1,4-dicarboxylic acid and the like, and mixturethereof.

Still another group comprises the epoxidized polyethylenicallyunsaturated hydrocarbons, such as epoxidized 2,2-bis(2-cyclohexenyl)propane, epoxidized vinyl cyclohexene and epoxidized dimerof cyclopentadiene.

Another group comprises the epoxidized polymers and copolymers ofdiolefins, such as butadiene. Examples of this include, among others,butadiene-acrylonitrile copolymers (Hycar rubbers), butadiene-styrenecopolymers and the like.

Another group comprises the glycidyl containing nitrogen compounds, suchas diglycidyl aniline and di-and triglycidylarnine.

The polyepoxides that are particularly preferred for use in thecompositions of the invention are the glycidyl ethers and particularlythe glycidyl ethers of polyhydric phenols and polyhydric alcohols. Theglycidyl ethers of polyhydric phenols are obtained by reactingepichlorohydrin with the desired polyhydric phenols in the presence ofalkali. Polyether A and Polyether B described in the above-noted US.Pat. No. 2,633,458 are good examples of polyepoxides of this type.

.Other examples include the polyglycidyl ether of l,l,2,2-

tetrakis (4-hydroxyphenyl)ethane (epoxy value of 0.45eq/ 100 and meltingpoint C), polyglycidyl ether of l,l,5,5-tetrakis(hydroxyphenyl)pentane(epoxy value of 0.514 eq/IOOg and the like and mixtures thereof. Otherexample include the glycidated novolacs as obtained by reactingepichlorohydrin with novolac resins obtained by condensation of aldehydewith polyhydric phenols.

The second component to be used in preparing the new reaction productsof the present invention are reactive, carboxyl group containingpolymers which contain a plurality of free carboxyl groups. Thesepolymers may be high molecular weight products, but preferably havemolecular weights varying from 2,000 up to about $00,000 as determinedby the light scattering technique. The carboxyl groups present in thepolymer molecular may be on the terminal monomer units or may be ininternal positions. The carboxyl groups may be inserted in the polymermolecular by a variety of techniques, such as by conversion of the CNgroup of carboxyl groups or by use of monomers in the initialpolymerization, such as acrylic or methacrylic acids. Other monomers mayalso be utilized in the formation of the polymers, such as, for exampleother monomers containing ethylenic groups, such as butadiene, isoprene,dimethylpentadine, ethylene propylene, methacrylonitrile, methylacrylate, ethyl acrylate, styrene, alpha-methylstyrene, chlorostyrene,vinylpyridine allyl alcohol, vinyl acetate, vinyl butyrate, allylacetate, diallyl phthalate, divinyl succinate, vinyl chloride,vinylidene chloride, ethylene glycol dimethacrylate, methylmethacrylate, butyl methacrylate, dihydroxybutyl methacrylate, and thelike and mixtures thereof. These other monomers are preferably utilizedin amounts varying from 90 to 1 percent by weight of the monomer. Theabove polymers may be prepared by any conventional technique, such asheating the monomers, alone or in the presence of a solvent, such asbenzene or xylene, in the presence of a free radical yielding catalyst,such as hydrogen peroxide, ditertiary butyl peroxide, tertiary butylperbenzoate, tertiary butyl peracetate, tertiary butyl perbutyrate andthe like. These catalysts are preferably utilized in amounts varyingfrom 0.1 to 5 percent by weight. Temperatures employed in thepolymerization depend on the decomposition temperature of the catalystand preferably vary from about 60 to about 150 C.

Particularly preferred polymer to be utilized comprises a polymer ofacrylonitrile and butadiene having a molecular weight ranging from about2,000 to 10,000 and having a plurality of free carboxyl groupsdistributed on the polymer chain. Also of special interest are theterpolymers made up of acrylonitrile, butadiene and methacrylic acidhaving a molecular weight from 3,000 to about 500,000.

The amount of reactive carboxyl group containing polymers which may beused in the present invention ranges from about 5-35 percent andpreferably about -20 percent by weight of the polyepoxide.

The compositions described in the present invention are prepared byreacting the 2,2-bis(4-hydroxyphenyl)sulfone and a reactive, carboxylgroup containing polymer with the polyepoxide in the presence of thehereinafter described catalysts. Catalysts which may be used in thepreparation of the reaction product include tertiary amines, quaternaryammonium salts, organo-substituted phosphine and phosphonium halides.

The tertiary amines that may be used as catalysts are those monoorpolyamines having an open chain or cyclic structure which have all ofthe amine hydrogen replaced bysuitable substituents, such as hydrocarbonradicals and preferably aliphatic, cycloaliphatic or aromatic radicals.

Examples of these amines include, among others, methyl diethanol amine,triethylamine, tributylarnine, dimethyl benzylamine, tripheylamine,tricyclohexylarnine, pyridine, quinoline, and the like. Preferred aminesare the trialkyl, tricycloalkyl and triaryl amines such astriethylamines, triphenylamines, tri(2,3-dimethylcyclohexylo)amine, andthe alkyl dialkanol amines, such as methyldiethanol amines. Weaktertiary amines, e.g., amines that in aqueous solutions give a pH lessthan 10, are particularly preferred.

The quaternary ammonium salts that may be used as catalysts for thereaction are preferably those of the formula wherein Y is nitrogen, X isan ion of an inorganic acid, and R is a hydrocarbon radical, such as analkyl, cycloalkyl, aryl, alkaryl, arylalkyl, and the like radicals.Examples of these salts include, among others, benzyltrimethylammoniumchloride, benzyltrimethylammonium sulfate, benzyltrimethylammoniumnitrate, diphenyldimethylammonium borate, diphenyldimethylammoniumnitrate and the like.

Particularly preferred quaternary ammonium salts are those of the aboveformula wherein R is an alkyl, aryl, or arylalkyl radical, preferablycontaining no more than 12 carbon atoms and X is a chlorine or bromine,such as benzyltrimethylammonium chloride, benzyltrimethylammoniumbromide, cyclohexyltrimethylammonium bromide, phenyltrioctylammoniumchloride and tetraoctylammonium chloride.

The organo-substitued phosphines that may be used as catalysts may beexemplified by the formula P(R) wherein at least one R is an organicradical and the other R's are hydrogen or organic radicals which may bethe same or different from the first R. Preferred phosphines include thetrihydrocarbyl phosphines, the dihydrocarbyl phosphines andmonohydrocarbyl phosphines, such as tricyclohexyl phosphine, tripenylphosphine, trioctyl phosphine, diphenyl cyclohexyl diphenyl phosphine,tributyl phosphine, trixylyl phosphine, tridodecyl phosphine, cyclohexyloctyl phosphine and the like. Particularly preferred phosphines includethe trialkyl, the tricycloalkyl, the tri(alkylcycloalkyl), and thetriaryl and tri(alkaryl) phosphines and particularly those wherein eachof the hydrocarbon radicals attached to the phosphorus atom contains nomore than 12 carbon atoms, and still more preferably no more than eightcarbon atoms, with a total number of carbon atons preferably not beingmore than 30. Coming under special consideration, particularly becauseof their high degree of activity as catalysts are the aromatichydrocarbyl phosphines as triphenyl phosphine.

The phosphonium halides that may be used as catalyst for the reactionare those preferably having the formula wherein X is a halogen atom, andR R R and R are the same or different and represent hydrocarbon residueswhich may or may not be substituted by one or more functional groups,such as halogen atoms. These phosphonium halides may generally beprepared by mixing in approximately equimolar proportions, a phosphinewith a halide. A more detailed description of the phosphonium halidesmay be found in US. Pat. No. 3,477,990 and such part of that patentwhich describes the phosphonium halides is hereby incorporated byreference.

These catalysts are preferably used in amounts preferably varying fromabout 0.05 to 3 percent by weight of the reactants.

Temperatures employed in the reaction will generally vary from about 50to about C. In most cases, the elastomeric components and thepolyepoxides will be quiet reactive and temperatures of the order ofabout 50to 125C will be suffcient to effect the desired reaction. Inother instances, it may be desirable to use higher temperatures, such asthose from 125 to C. Temperatures of 200 C. or over should generally notbe employed.

The reaction is preferably conducted under atmospheric pressure, but maybe advantageous in some cases to employ subatmospheric orsuperatmospheric pressures.

The reaction may be conducted in the presence or absence of solvents ordiluents, though it is generally effected without the addition ofsolvents or diluents. In some cases, when some of the reactants aresolids or viscous liquids it may be desirable to add diluents to assistin effecting the reaction, such as, for example, inert hydrocarbons aszylene, toluene, cylohexane, and other materials as cyclohexanone, andthe like.

As the compositions of the present invention possess epoxy groups, theymay be cured with epoxy curing agents to form insoluble infusibleproducts. For this purpose, epoxy curing agents which are acidic,neutral or alkaline may be added. Examples of the curing agents include,among others, amines, polybasic acids and polybasic acid anhydrides,polymercaptans, amino-containing polyarnides, diazonium salts, metalsalts, amine salts, etc. Examples of the curing agents include, amongothers, meta-phenylene diarnine, dicyandiamide, diethylene triamine,ethylene diarnine, diamino-diphenyl-sulfone, salts, such as zincfluoborate, magnesium perchlorate and zinc fluosilicate; phosphoric acidand partial esters thereof including n-butyl ortho-phosphate, diethylorthophosphate hexaethyl tetraphosphate; triethylene tetramine,melamine, pyridine, cyclohexylamine, benzyldimethyl-amine, benzylamine,diethylaniline, triethanolarnine, piperidine, tetramethyl piperazine,N,N-diethyll l ,3-propane diamine, l,2diamino-2-methylpropane,2,3-diamino-2- methylbutane, 2,4-diamino-2-methylpentane, 2,4-diamino-2,o-dimethylocatane, dibutylamine, dinonylamine, distearylarnine, diallylamine, dicyclohexylamine, ethylcyclohexylamine, O-tolylnapthtylamine,pyrrolidine, 2- methyl-pyrrolidine, tetrahydropyridine,2-methylpiperdine, 2,6-dimethyl-piperidine, diaminopyridine,tetramethylpentane, metaphenylene diamine, and the like, and solubleadducts of amines and polyepoxides and their salts, such as described inUS. Pat. No. 2,651,589 and US. Pat. No. 2,640,037. Preferred curingagent are the amines and preferably the aromatic monoand diamines.

Accelerators may also be used in conjunction with curing agents in thepresent invention. Accelerators act to hasten cure and includesubstituted imidazoles and salts thereof, such as, for example,2-ethyl-4-methylimidazole and the lactic acid salt of irnidazole. Acetylguanidine and p-chlorophenyl-l,ldimethylurea may also be used.Accelerators are used in amounts of 140 parts and preferably 5-20 partsby weight of curing agent.

Theamount of the curing agent employed may vary widely. In general, theamount of the curing agent will vary from about 0.5 to 200 percent byweight of the polyepoxide. The tertiary amines and BF -complexes arepreferably employed in amounts varying from about 0.5 to 20 percent andthe metal salts are preferably employed in amounts varying from about 1percent to percent. The secondary and primary amines, acids andanhydrides are preferably employed in at least stoichiometric amounts,i.e., sufficient amount to furnish one amine hydrogen for one anhydridegroup for every epoxy group, and more preferably stoichiometric ratiosvarying from 1:1 to 25:1.

The third component to be used in preparing the present invention is2,2-bis(4-hydroxyphenyl)sulfone (Bisphenol S):

BISPHENOL S Bisphenol S is a commercially available compound (VVITCOChemical Company) available in 99 percent 4,4isomer purity, having 99percent active sulfone and a melting point of 245-248 C. The amount ofBisphenol S which may be used in the present invention ranges from about5-35 percent and preferably from about 15-25 percent by weight of thepolyepoxide.

The compositions of the present invention are useful in a great varietyof difierent applications, such as in preparing adhesives and the like.The compositions may be used for bonding materials, such asglass-to-glass, metal-to-metal, glass-tometal, wood-to-wood, and thelike. They are particularly valuable as adhesives for bonding glasscloth to glass, and metal to glass, for example, when applied to thedesired surfaces to form films of various thickness, e.g., 5 mils to 30mils and then the other surfaces superimposed and heat and/or pressureap plied. The two surfaces may be also placed in a fixed positionrelative toeach other and the adhesive forced between the surfaces,pressure applied, and the assembly heated to about 100 to 300 C toeffect cure.

The compositions are of value as adhesives for metal-tometal bonding. Inthis case, it has been found advantageous to impregnate cotton, rayon,and woven, knitted and non-woven cloth of synthetic fiber or glass clothtextiles with the composition, and then use the impregnated textile as abonding tape for joining the metals. Such tapes provide convenient meansfor'handling and using the compositions in adhesive applications. Thetape is inserted between two metals to be joined, and the assembly isthen preferably heated to speed the cure of the resin. A preferred tapefor such use has a nylon fiber textile impregnated with a mixturecontaining the adduct, an amine curing agent, silica and/or asbestosfiller.

The compositions are also useful for preparing surface coatingcompositions. ln this application, the composition is usually mixed withone or more of suitable solvents or diluents, such as, for example,ketones, such as methyl isobutyl ketone, acetone, methyl ethyl ketone,isophorone, esters, such as ethyl acetone, cellosolve acetate (ethyleneglycol monoacetate), methyl cellosolve acetate (acetate of ethyleneglycol monoethyl ether), etc.; ether alcohols, such as methyl, ethyl, orbutyl ether of ethylene glycol or diethylene glycol, chlorinatedhydrocarbons, such as trichloropane; hydrocarbons, such as benzene,toluene, xylene and the like, to give a mixture having suitableviscosity for spraying, brushing or dipping, and then the necessarycuring agent as described above may be added alone or in admixture witha suitable solvent. The cure of the coating compositions thus preparedmay be preferably accomplished by the application of heat. Satisfactorycures are obtained generally with temperatures of 60 up to 200C.

Additional materials may be added in the preparation of the coatingcompositions to vary the properties. Such materials include pigments,dyes, stabilizers, plasticizers and various bonding agents as oils,resins and tars. Materials such as coal tars, asphalts, and the like areparticularly desirable for use when the coatings are to be employed forthe treatment of roadways, floors and the like.

The coatings prepared from the compositions of the invention arecharacterized, as noted above, by their toughness, chemical resistance,good adhesion and improved high temperature shear strength.

Another important application of the products of the invention is in theproduction of laminate or resins or resinous articles reinforced withfibrous materials. Although it is generally preferred to utilize glasscloth for this purpose, any of the other suitable fibrous materials insheet form may be employed, such as glass matting, paper, asbestospaper, mica flakes, cotton bats, duck muslin, canvas, and the like.

In preparing the laminate, the sheets of fibrous material are firstimpregnated with the mixture containing the composition described in thepresent invention and curing agent. This may be accomplished by ahot-metal technique or by dissolving the composition and curing agent inacetone or a suitable solvent. In the latter instance, the sheets offibrous material are then impregnated with the mixture by spreading itthereon or by dipping or otherwise immersing them in the impregnant. Thesolvent is conveniently removed by evaporation and the mixture is curedby the application of heat as noted above.

Another important use of the compositions of the invention is theproduction of molded articles. A molding powder is first prepared bymilling together a mixture of the composition and curing agent withcustomary fillers and mold release agents. Usually the milled mixture isset up so that a fusible resin is first obtained. The milled mixture isthen ground and molded articles obtained therefrom with conversion ofthe fusible resin into the infusible state with use of molding machinessuch as those for compression molding or transfer molding. If desired,fusible milled mixture may be prepared in pre-form pellets and the like.

To illustrate the manner in which the invention may be car ried out, thefollowing examples are given. It is to be understood that the examplesare for the purpose of illustration and the invention is not to beregarded as limited to any of the specific compounds or conditionsrecited therein. Unless otherwise specified, parts disclosed in theexamples are parts by weight. Polyether A referred to in the examples isPolyether A described above.

EXAMPLE 1 Two formulations were prepared as follows:

FORMULATION l 2 l) Polyether A: Diglycidyl ether of2,2-bis(4-hydroxyphenyl)propane having an epoxide equivalent of 175-210(grams of resin containing one gram-equivalent of epoxide) and amolecular weight of about 380. (2) Bisphenol S:2,2-bis(4-hydroxyphenyl)sulfone (3) Catalyst: Triphenyl Phosphine (4)Carboxyl group containing polymer: Acrylonitrile-butadiene copolymerhaving a molecular weight of 3365, an acrylonitrile content of about80%, a carboxyl equivalency of 1540 (functionality of 2.34) andunsaturation in the polymer of 16.3% cis, 68.7% trans and 15% vinyl.

(5) Accelerator: 2-ethyl-4-methylimidazole (6) Bisphenol A:2,2-bis(4-hydroxyphenyl)propane (7) Curing agent: DicyandiamideFormulations l and 2 were then identically prepared as follows:

The Polyether A, Bisphenol S (in Formulation I), Bisphenol A (inFormulation 2), catalyst and carboxyl group containing polymer werecombined and heated for one hour at between 130 and 160C. The resultingreaction products were soluble in acetone. To these reaction productswas added the curing agent and accelerator.

Tapes were made by spreading the mixtures as a thin film (about 3.5mils) on both sides of a knitted nylon cloth. The following testspecimens were assembled and cured for 1 hour at 250F. Table 1 belowtabulates the resulting data from the testing of the specimens.

TABLE 1 FORMULATION l 2 Tensile Shear Strength (psi) EXAh/[PLE 11 TwoFormulations were prepared as follows:

FORMULATION 3 4 Polyether A 103.5 103.5 Rubber copolymer 5.0 5.0Carboxyl Group Containing Polymer 10.0 10.0 Bisphenol A 21.0 Bisphenol S23.0 Catalyst 0.2 0.2 Curing agent 8.0 8.0 Acceleratol 1.0 1.0

( l) Polyether A: Footnote 1, EXAMPLE 1.

( 2) Rubber Copolymer: A solid acrylonitrile-butadiene copolymer havinga molecular weight of 300,000 and an acrylonitrile content of about (3)Carboxyl Group Containing Polymer: Footnote 4, EXAMPLE I. (4) BisphenolA: Footnote 6, EXAMPLE I.

(5) Bisphenol S: Footnote 2, EXAMPLE I.

(6) Catalyst: Triphenyl Phosphine (7) Curing agent: Dicyandiamide (8)Accelerator: p-chlorophenyl-l I -dimethylurea Formulations 3 and 4 werethen identically prepared as follows:

The Polyether A, Bisphenol S (in formulation 4), Bisphenol A (informulation 3) catalyst, rubber copolymer and carboxyl group containingpolymer were combined and heated for 1 hour at 150C. The resultingreaction products were soluble in acetone. To these reaction productswere added the curing agent and accelerator.

Tapes were made by spreading these mixtures as a thin film (5mils) onboth side of nylon cloths. The following test specimens were assembledand cured for 1 hour at 250C and 25 psi. Table 2 below tabulates theresulting data from the testing of the specimens.

TABLE 2 FORMULATION 3 4 Tensile Shear Strength (psi) EXAMPLE III ExampleI is repeated except that equivalent amounts of the followingpolyepoxides are utilized instead of polyether A: Polyglycidyl ether ofphenol-formaldehyde novolac (DEN 438), a phenoxy copolymer of BisphenolA and Epichlorohydrin (PKDA-8500) EPON 1001 and the diglycidyl ether oftetrabromobisphenol A (DER 542). Related results are achieved.

(1) DEN 438: polyphenol-formaldehyde poly(2,3-epoxypropyl)ether. Epoxyeq/ 1 00g of 0.56.

(2) PKDA-8500: MW of about 25,000, Secondary hydroxyl: 6% by weight.

(3) EPON I001: Glycidyl ether of 2,2-bis(4-hydroxyphenyl) propane havingan epoxy eq/ g of 0.23. (4) DER 542: 2,2-bis[4-(2,3-epoxypropoxy)-3,5-

dibromophenyl]propane. Epoxy eq/ 100g of 0.28.

EXAMPLE IV Example I is repeated, except that the following curingagents are used instead of dicyandiamide: melamine, dimethyldiphenylsulfone and M-phenylene diamine. Related results are achieved.

EXAMPLE V Example I is repeated, except that the following catalysts areused instead of triphenyl phosphine: benzyltrimethylammonium chloride,methyl diethanol amine and triethyl amine. Related results are achieved.

We claim:

1. An epoxy-containing composition comprising the acetone solublereaction product of a major amount of a polyepoxide having more than one1,2 epoxy group per molecule and about -35 percent by Weight of acarboxyl group containing addition copolymer and about 5-35 percent byweight of 2,2-bis(4-hydroxyphenyl)sulfone.

2. A composition suitable for use as an adhesive comprising the reactionproduct of claim 1 additionally containing an epoxy curing system.

3. An insoluble infusible product obtained by heating the composition ofclaim 2 at a temperature between about 50 and 200C.

4. A composition as in claim 2 wherein the polyepoxide is a liquidglycidyl polyether of a polyhydric phenol.

5. A composition as in claim 4 wherein the polyhydric phenol is 2,2-bis(4-hydroxyphenyl)propane.

6. A composition as in claim 2 wherein the epoxy curing system includesan accelerator.

7. A composition as in claim 2 wherein the reactive, carboxyl groupcontaining polymer is a polymer which contains at least percent byweight of acrylonitrile units and a plurality of free carboxyl groups.

8. A composition as in claim 7 wherein the reactive, carboxyl groupcontaining polymer is a copolymer of acrylonitrile and butadiene havinga plurality of free carboxyl groups distributed on the polymer chain.

9. An insoluble, infusible epoxy containing composition comprising thecured reaction product of a major amount of the diglycidyl ether of2,2-bis(4-hydroxylpenyl)propane, and about 5-35 percent by weight of acopolymer of acrylonitrile and butadiene having a plurality of freecarboxyl groups and about 5-35 percent by weight of2,2-bis(4-hydroxyphenyl)sul- 10 fone.

10. A process for preparing an acetone soluble epoxy-containingcomposition which comprises reacting at a temperature of about 50-l 75C.

1. a major amount of a polyepoxide having more than one 1,2 epoxy groupper molecule with 2. about 5-35 percent by weight of a carboxyl groupcontaining addition copolymer in the presence of from 0.05 to 3 percentby weight of the reactants of a catalyst selected from the groupconsisting of tertiary amines, quaternary ammonium salts,organo-substituted phosphine and phosphonium halides and 3. about 5-35percent by weight of 2,2-bis(4-hydroxyphenyl)sulfone.

11. A process as in claim 10 wherein the polyepoxide is a glycidylpolyether of a polyhydric phenol.

12. A process as in claim 10 wherein the catalyst is triphenylphosphine.

13. A process as in claim 12 wherein the polyepoxide is the glycidylpolyether of 2,2-bis(4-hydroxyphenyl)-propane.

14. A process as in claim 10 wherein the reactive, carboxyl groupcontaining polymer is a polymer which contains at least 10 percent byweight of acrylonitrile units and a plurality of free carboxyl groups.

15. A process as in claim 13 wherein the reactive, carboxyl groupcontaining polymer is a copolymer of acrylonitrile and butadiene havinga plurality of free carboxyl groups distributed on the polymer chain.

2. A composition suitable for use as an adhesive comprising the reactionproduct of claim 1 additionally containing an epoxy curing system. 2.about 5-35 percent by weight of a carboxyl group containing additioncopolymer in the presence of from 0.05 to 3 percent by weight of thereactants of a catalyst selected from the group consisting of tertiaryamines, quaternary ammonium salts, organo-substituted phosphine andphosphonium halides and
 3. about 5-35 percent by weight of2,2-bis(4-hydroxyphenyl)sulfone.
 3. An insoluble infusible productobtained by heating the composition of claim 2 at a temperature betweenabout 50* and 200*C.
 4. A composition as in claim 2 wherein thepolyepoxide is a liquid glycidyl polyether of a polyhydric phenol.
 5. Acomposition as in claim 4 wherein the polyhydric phenol is2,2-bis(4-hydroxyphenyl)propane.
 6. A composition as in claim 2 whereinthe epoxy curing system includes an accelerator.
 7. A composition as inclaim 2 wherein the reactive, carboxyl group containing polymer is apolymer which contains at least 10 percent by weight of acrylonitrileunits and a plurality of free carboxyl groups.
 8. A composition as inclaim 7 wherein the reactive, carboxyl group containing polymer is acopolymer of acrylonitrile and butadiene having a plurality of freecarboxyl groups distributed on the polymer chain.
 9. An insoluble,infusible epoxy containing composition comprising the cured reactionproduct of a major amount of the diglycidyl ether of2,2-bis(4-hydroxylpenyl)propane, and about 5-35 percent by weight of acopolymer of acrylonitrile and butadiene having a plurality of freecarboxyl groups and about 5-35 percent by weight of2,2-bis(4-hydroxyphenyl)sulfone.
 10. A process for preparing an acetonesoluble epoxy-containing composition which comprises reacting at atemperature of about 50*-175*C.
 11. A process as in claim 10 wherein thepolyepoxide is a glycidyl polyether of a polyhydric phenol.
 12. Aprocess as in claim 10 wherein the catalyst is triphenyl phosphine. 13.A process as in claim 12 wherein the polyepoxide is the glycidylpolyether of 2,2-bis(4-hydroxyphenyl)-propane.
 14. A process as in claim10 wherein the reactive, carboxyl group containing polymer is a polymerwhich contains at least 10 percent by weight of acrylonitrile units anda plurality of free carboxyl groups.
 15. A process as in claim 13wherein the reactive, carboxyl group containing polymer is a copolymerof acrylonitrile and butadiene having a plurality of free carboxylgroups distributed on the polymer chain.